JPH0582812B2 - - Google Patents
Info
- Publication number
- JPH0582812B2 JPH0582812B2 JP60186031A JP18603185A JPH0582812B2 JP H0582812 B2 JPH0582812 B2 JP H0582812B2 JP 60186031 A JP60186031 A JP 60186031A JP 18603185 A JP18603185 A JP 18603185A JP H0582812 B2 JPH0582812 B2 JP H0582812B2
- Authority
- JP
- Japan
- Prior art keywords
- vulcanization
- fkm
- nbr
- compound
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004073 vulcanization Methods 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 16
- 239000005060 rubber Substances 0.000 claims description 16
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 150000004714 phosphonium salts Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000009472 formulation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010060 peroxide vulcanization Methods 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229920002449 FKM Polymers 0.000 description 36
- 239000010410 layer Substances 0.000 description 30
- 229920000459 Nitrile rubber Polymers 0.000 description 28
- 239000000463 material Substances 0.000 description 8
- -1 FKM compound Chemical class 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- PZQOTJJEMXLHKG-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoropropan-2-ylidene)-5,6-bis(4-hydroxyphenyl)cyclohexa-1,5-diene-1,4-diol Chemical compound FC(C(C(F)(F)F)=C1C(C(=C(C(O)=C1)C1=CC=C(C=C1)O)C1=CC=C(C=C1)O)O)(F)F PZQOTJJEMXLHKG-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LUPPVMGFWRYTLW-UHFFFAOYSA-N 5,6-bis(4-hydroxyphenyl)-3-propan-2-ylidenecyclohexa-1,5-diene-1,4-diol Chemical compound OC1C(=C(C)C)C=C(O)C(C=2C=CC(O)=CC=2)=C1C1=CC=C(O)C=C1 LUPPVMGFWRYTLW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- YGPAXTKKXYABEL-UHFFFAOYSA-M benzyl(triphenyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 YGPAXTKKXYABEL-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- AXTXARBFPWQUQA-UHFFFAOYSA-M tetraoctylphosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC AXTXARBFPWQUQA-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Description
<産業上の利用分野>
本発明は、FKM層とNBR層とが加硫接着され
てなるゴム積層体の製造方法に関し、自動車用燃
料ホース、フユエルポンプ用ダイアフラム等とし
て好適なものである。
この明細書において、「FKM」はフツ素ゴム
の、「NBR」はニトリルゴムのそれぞれ略号であ
る。また、「PHR」は、ゴム分(ポリマー)に対
する外掛重量百分率のことである。
<従来の技術>
FKMは、耐熱性、耐薬品性、耐老化性、耐寒
性等の諸物性に優れ、油、燃料などにも強いた
め、上記の燃料ホースやダイアフラム、さらには
耐薬品用ホース・パツキン等の素材として着目さ
れているが、コストがNBR等の汎用ゴムに比し
て10〜20倍と高価で使用箇所が限定される。この
ためFKMを燃料ホース等の素材として使用する
に際して、耐油性の比較的良好な汎用ゴムである
NBR層を基体層として、より高度の諸物性を要
求される側にFKM層を加硫接着して使用するこ
とが考えられるが、一般にFKM層とNBR層と
は、通常の方法では、加硫接着することは困難で
あつた。特に、FKM層が過酸化物加硫系の配合
物からなる場合、この傾向は、特に顕著であつ
た。尚、過酸化物加硫系のFKMは、他のポリア
ミン・ポリオール加硫系のFKMに比して、加硫
速度が大きくまた架橋密度も高くなることから二
次加硫なしでも良好な耐圧縮永久歪性(耐へたり
性)を得ることができる等の長所を有する。
そこで、特公昭57−49391号公報、特公昭59−
33304号公報等で、未加硫のNBR配合物におい
て、酸化マグネシウム、シリカなど金属酸化物を
含有させて接着性を改善する方法が提案されてい
るが、FKM層とNBR層との層間接着力は必ずし
も十分とは言えなかつた。
このため、本発明者らにより、過酸化物加硫系
のFKM配合物において、過酸化物加硫系の配合
剤に加えてポリオール加硫系に使用する加硫配合
剤が配合されたものからなるFKM層と、NBR配
合物において、金属酸化物が配合(加硫助剤とし
て金属酸化物《又は水酸化物》が含まれている場
合はそれに加えて)されたものからなるNBR層
とを加硫接着させた積層体が提案されている(特
開昭61− 号《特願昭60−87102》参
照)。
<発明が解決しようとする問題点>
上記ゴム積層体は、NBR層とFKM層との間に
大きな層間接着力を得るには、ポリオール加硫系
の加硫配合剤に含まれる加硫促進剤(有機ホスホ
ニウム塩/又は第四級アンモニウム塩)を多量に
配合する必要があるため、FKMに押出時や混練
時にスコーチが発生しやすく、またFKMの物性
の低下、特に耐溶剤亀裂性、耐寒性が悪くなると
いう問題があつた。
<問題点を解決するための手段>
そこで、本発明者らは、上記問題点を解決すべ
く、鋭意開発に努力した結果、ポリオール加硫系
の加硫配合剤が併せて配合されている過酸化物加
硫系のFKM配合物からなるFKM層と、金属酸化
物が特定量、及び、さらに上記ポリオール加硫系
の加硫配合剤中における加硫促進剤が特定量配合
されたNBR配合物からなるNBR層とを加硫接着
すれば、製造に際してFKMにスコーチが発生し
にくく、物性も良好でしかも、得られるゴム積層
体の層間接着力も良好であることを見い出し、本
発明のゴム積層体の製造方法を完成した。
<実施の態様>
下記FKM配合物〈A〉からなるFKM層1と、
下記配合物〈B〉からなるNBR層2とを加硫接
着させて製造する。ここで、加硫接着の方法は特
に限定されない。
例えば、第1図に示すようなゴムホースの場
合、1台又は2台の押出機より各配合物を同時又
は、別体に押出して積層したものを、適宜条件
(145〜170℃×30〜90min)で加硫接着を行なう。
また、第2図に示すようなダイヤフラムの場合、
各配合物をシート状にロール分出したものを打ち
抜き重ね合せてプレス成形(型温150〜190℃、時
間3〜30min、圧力50〜150kgf/cm2)して加硫接
着を行なう。なお図例中3は基布層を示す。尚、
ゴム積層体の構成は図例のものに限られず、例え
ば補強ホースや内外(表裏)FKM層としたホー
スやダイヤフラム、さらには総ゴムダイヤフラム
等に適用可能である。
〈A〉FKM配合物:下記FKMポリマー、過酸化
物加硫系加硫配合剤、ポリオール加硫系加硫配合
剤及び他の副資材からなる。
(1) FKM(ポリマー)は、過酸化物加硫可能にラ
ジカル活性な沃素又は臭素がポリマー中に導入
されておれば特に二元系、三元系限定されな
い。二元系としてフツ化ビニリデン・六フツ
化プロピレン共重合体、三元系としてフツ化
ビニリデン・六フツ化プロピレン・四フツ化エ
チレン三元共重合体をそれぞれ例示できる。さ
らに具体的には、上記はダイエルG801等の
商品名で、上記はバイトンGF、バイトン
GH、バイトンVTR5362、ダイエルG901、ダ
イエルG902等の商品名でそれぞれ上市されて
いる。なお、“バイトン”及び“ダイエル”は
それぞれデユポン社及びダイキン工業の商標で
ある。
(2) 過酸化物加硫系加硫配合剤には、加硫剤とし
ての有機過酸化物、共架橋剤としてのトリアリ
ルイソシアヌレート等の他に、他の加硫系にも
使用されるMgO等の受酸剤、Ca(OH)2等の無
機促進剤も含まれる。尚、FKM配合物には、
当然のことながら、カーボンブラツク等の補強
剤、加工助剤さらには適宜着色剤、スコーチ防
止剤等が配合される。
上記過酸化物としては、ジクミルペルオキシ
ド、2,5−ジメチル−2,5−ジ(t−ブチ
ルペルオキシ)ヘキサン、2,5−ジメチル−
2,5−ジ(t−ブチルペルオキシ)ヘキサン
−3、1,1−ビス(t−ブチルペルオキシ)
−3,3,5−トリメチルシクロヘキサン、t
−ブチルペルオキシベンゾエート等を例示で
き、その配合合量は通常1〜10PHRとする。
(3) ポリオール加硫系配合剤とは、加硫剤として
の芳香族ポリオール化合物と、加硫促進剤とし
ての有機ホスホニウム塩及び/又は第四級アン
モニウム塩(単独でも併用でも可)を組合わせ
たものである。ここで加硫剤(芳香族ポリオー
ル)の配合量は、通常1.3〜2PHR、加硫促進
剤の配合量は、ムーニー・スコーチ時間
(JISK6300,145℃)t5を4分以上で、耐溶剤
亀裂性が100秒以上、無破壊温度が−20℃以下
となる量に設定する。第1表より、有機ホスホ
ニウム塩、有機アンモニウム塩は0.7PHR以下
とする。
上記芳香族ポリオールとしては、ヘキサフル
オロイソプロピリデン−ビスー(4ヒドロキシ
フエニル)ヒドロキノン、イソプロピリデン−
ビス(4ヒドロキシフエニル)等を、有機ホス
ホニウム塩としては、トリフエニルベンジルホ
スホニウムクロライド、テトラフエニルホスホ
ニウムクロライド、テトラオクチルホスホニウ
ムクロライド等を、第四級アンモニウム塩とし
ては、トリフエニルベンジルアンモニウムクロ
ライド、テトラフエニルアンモニウムクロライ
ド等をそれぞれ挙げることができる。
(4) 他の副資材としては、補強剤としてのカーボ
ンブラツク、受酸剤としてMgO、Ca(OH)2、
可塑剤、さらには加工助剤などがあり、適宜配
合する。
〈B〉NBR配合物:下記NBRポリマーに加硫
剤、周期表第−族から選ばれる金属酸化物類
が他の副資材とともに配合され、さらに、上記
〈A〉における加硫促進剤(有機ホスホニウム塩
及び/又は第四級アンモニウム塩)FKM配合物
におけるポリオール加硫系加硫配合剤中に有機ホ
スホニウム塩を含む場合は、0.1〜2PHR、同じ
く第四級アンモニウム塩を含む場合は0.05〜
2PHRそれぞれ配合されている。
ここで、加硫促進剤の配合量が、下限数値未満
では、FKM層とNBR層との間に大きな層間接着
力を得がたく、上限数値を超えても層間接着力は
増大せず無駄である。
(1) NBRは、アクリルニトリル・ブタジエン共
重合体であるが、通常NBR層の耐油性、耐寒
性の観点からアクリルニトリルの結合量15〜55
%のものを用いる。具体的には、ニポール
DN101・103・202・302・206、TN103、
JSRN220S・N230S・N231H、ハイカー
1001・1031・1042等の商品名で上布されている
ものを挙げることができる。ここで、“ニポー
ル”及び“ハイカー”は日本ゼオンの、“JSR”
は日本合成ゴムのそれぞれ商標である。
(2) このNBRの加硫系は、硫黄加硫、過酸化物
加硫等、特に限定されていない。尚、過酸化物
加硫剤としては前述に例示のものを使用する。
(3) 金属酸化物類としては、酸化マグネシウム、
酸化アルミニウム、酸化亜鉛、二酸化亜鉛、酸
化カルシウム、酸化鉛(,)、二酸化ケイ
素等及びこれらの水酸化物を例示でき、特にこ
れらの内で酸化マグネシウム、水酸化カルシウ
ム、水酸化アルミニウム、酸化鉛、()が好
ましい。この金属酸化物類の配合量は通常5〜
30PHRとする。
(4) 上記以外の副資材としては、カーボンブラツ
ク等の補強剤、加硫促進剤、加工助剤、可塑
剤、着色剤、老化防止剤等があり、適宜配合す
る。
<発明の効果>
本発明のゴム積層体の製造方法は、上記の如
く、NBR配合物中にもFKM配合物中に含まれる
ポリオール加硫系加硫配合剤における加硫促進剤
を特定量配合することにより、製造に際して、押
出時や混練時、カレンダー時にFKMにスコーチ
が発生しにくく、材料物性も良好でしかも、得ら
れるゴム積層体の層間接着力も、後述の実施例で
示すが如く良好である。
<実施例>
各試験例の調整は、第1表に示す処方の配合物
でFKM層を、第2表に示す処方の配合物でNBR
層を、それぞれ4mmtのシート状にロール分出し
たものを、第3表に示す組合せで、170℃×15分、
150Kgf/cm2の条件で加圧加硫した。接着力は
JISK6301の“はく離試験”に準じて測定した。
なお、各FKM及びNBRのスコーチ時間
(JISK6300,145℃)常態物性(JISK6301)、耐
溶剤亀裂性及び低温衝撃ぜい化試験(JISK6301)
も測定したので、第1・2表にそれらの結果を示
す。なお、耐溶剤亀裂性は、JISダンベル1号形
試験片を50%伸張状態でフユエルD(トルエン
60vol%/イソオクタン40vol%)中に浸せきし、
破断までの時間を測定した。
第3表に示す結果から、NBRにポリオール加
硫系の加硫配合剤における加硫促進剤を特定量以
上(FKMに有機ホスホニウム塩が配合されてい
るときは0.1PHR以上、同じく第四級アンモニウ
ム塩が配合されているときは0.05PHR以上)配
合したときは(N−2・3・4・5・6)、FKM
層とNBR層との間に良好な層間接着力が発生す
るとがわかる。また、第2表からNBRにポリオ
ール加硫系の加硫促進剤を配合してもスコーチ時
間は影響を受けないことがわかる。なお、第1表
に示すが如く、F1〜F3,F6〜F7のFKMはいず
れもスコーチ時間が7分以上である。
<Industrial Field of Application> The present invention relates to a method for producing a rubber laminate in which an FKM layer and an NBR layer are vulcanized and bonded, and is suitable for use in automobile fuel hoses, fuel pump diaphragms, and the like. In this specification, "FKM" is an abbreviation for fluororubber, and "NBR" is an abbreviation for nitrile rubber. Moreover, "PHR" refers to the outer weight percentage relative to the rubber content (polymer). <Conventional technology> FKM has excellent physical properties such as heat resistance, chemical resistance, aging resistance, and cold resistance, and is resistant to oil and fuel.・It is attracting attention as a material for packing materials, etc., but it is 10 to 20 times more expensive than general-purpose rubber such as NBR, and its usage is limited. Therefore, when using FKM as a material for fuel hoses, etc., it is a general-purpose rubber with relatively good oil resistance.
It is conceivable to use the NBR layer as a base layer by vulcanizing and adhering the FKM layer to the side that requires higher physical properties, but in general, the FKM layer and the NBR layer are separated by vulcanization. It was difficult to adhere. In particular, this tendency was particularly pronounced when the FKM layer was composed of a peroxide-cured compound. Furthermore, peroxide-cured FKM has a faster vulcanization rate and higher crosslinking density than other polyamine/polyol-cured FKMs, so it has good compression resistance even without secondary vulcanization. It has advantages such as being able to obtain permanent deformation (settling resistance). Therefore, Special Publication No. 57-49391, Special Publication No. 59-
Publication No. 33304 and other publications propose a method of improving adhesion by incorporating metal oxides such as magnesium oxide and silica into unvulcanized NBR compounds, but the interlayer adhesion between the FKM layer and the NBR layer was not necessarily sufficient. For this reason, the present inventors have developed a peroxide vulcanization FKM formulation containing a vulcanization compound used in a polyol vulcanization system in addition to a peroxide vulcanization compound. and an NBR layer made of an NBR compound containing a metal oxide (if a metal oxide (or hydroxide) is included as a vulcanization aid, in addition to it). A laminate bonded by vulcanization has been proposed (see Japanese Patent Application Laid-open No. 1987-87102). <Problems to be Solved by the Invention> In order to obtain a large interlayer adhesive force between the NBR layer and the FKM layer, the above rubber laminate requires a vulcanization accelerator contained in a polyol vulcanization-based vulcanization compound. Because it is necessary to incorporate a large amount of (organic phosphonium salt/or quaternary ammonium salt), scorch is likely to occur in FKM during extrusion or kneading, and the physical properties of FKM deteriorate, especially solvent cracking resistance and cold resistance. I had a problem with it getting worse. <Means for Solving the Problems> Therefore, in order to solve the above problems, the present inventors made earnest efforts in development, and as a result, the inventors of the present invention have developed a superfluous resin containing a polyol vulcanization-based vulcanization compounding agent. An NBR compound containing an FKM layer consisting of an oxide vulcanization-based FKM compound, a specific amount of a metal oxide, and a specific amount of a vulcanization accelerator in the above-mentioned polyol vulcanization-based vulcanization compound. It has been found that if the rubber laminate of the present invention is vulcanized and bonded with the NBR layer, scorch is less likely to occur in the FKM during production, the physical properties are good, and the resulting rubber laminate has good interlayer adhesion. Completed the method for manufacturing the body. <Embodiment> FKM layer 1 consisting of the following FKM compound <A>,
It is manufactured by vulcanizing and adhering NBR layer 2 consisting of the following compound <B>. Here, the method of vulcanization adhesion is not particularly limited. For example, in the case of a rubber hose as shown in Figure 1, each compound is extruded simultaneously or separately from one or two extruders and laminated, then laminated under appropriate conditions (145-170℃ x 30-90min). ) to perform vulcanization adhesion.
In addition, in the case of a diaphragm as shown in Figure 2,
Each compound is rolled out into sheets, which are then punched out and stacked on top of each other, and then press-molded (mold temperature: 150-190°C, time: 3-30 min, pressure: 50-150 kgf/cm 2 ) to perform vulcanization bonding. Note that 3 in the illustrated example indicates the base fabric layer. still,
The configuration of the rubber laminate is not limited to the illustrated example, and can be applied to, for example, reinforced hoses, hoses and diaphragms with FKM layers on the inside and outside (front and back), and even full rubber diaphragms. <A> FKM compound: Consists of the following FKM polymer, peroxide vulcanization type vulcanization compound, polyol vulcanization type vulcanization compound and other auxiliary materials. (1) FKM (polymer) is not particularly limited to binary or ternary type as long as radically active iodine or bromine is introduced into the polymer to enable peroxide vulcanization. Examples of the binary system include vinylidene fluoride/propylene hexafluoride copolymer, and examples of the ternary system include vinylidene fluoride/propylene hexafluoride/ethylene tetrafluoride terpolymer. More specifically, the above are product names such as Daiel G801, and the above are Viton GF, Viton
They are marketed under product names such as GH, Viton VTR5362, Daiel G901, and Daiel G902. Note that "Viton" and "Daiel" are trademarks of DuPont and Daikin Industries, respectively. (2) In addition to organic peroxide as a vulcanizing agent and triallylisocyanurate as a co-crosslinking agent, peroxide vulcanization-based vulcanization compounds can also be used in other vulcanization systems. Also included are acid acceptors such as MgO and inorganic accelerators such as Ca(OH) 2 . Furthermore, FKM formulations include:
Naturally, reinforcing agents such as carbon black, processing aids, and optionally coloring agents, scorch inhibitors, etc. are blended. Examples of the peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-
2,5-di(t-butylperoxy)hexane-3,1,1-bis(t-butylperoxy)
-3,3,5-trimethylcyclohexane, t
-Butyl peroxybenzoate, etc. can be exemplified, and the amount thereof is usually 1 to 10 PHR. (3) A polyol vulcanization compound is a combination of an aromatic polyol compound as a vulcanizing agent and an organic phosphonium salt and/or quaternary ammonium salt (can be used alone or in combination) as a vulcanization accelerator. It is something that The blending amount of the vulcanizing agent (aromatic polyol) is usually 1.3 to 2 PHR, and the blending amount of the vulcanization accelerator is Mooney scorch time (JISK6300, 145℃) t 5 for 4 minutes or more, solvent crack resistance. Set the amount so that the resistance is 100 seconds or more and the non-destructive temperature is -20℃ or less. From Table 1, the organic phosphonium salt and organic ammonium salt should be 0.7 PHR or less. The aromatic polyols include hexafluoroisopropylidene-bis(4-hydroxyphenyl)hydroquinone, isopropylidene-bis(4-hydroxyphenyl)hydroquinone,
bis(4-hydroxyphenyl), organic phosphonium salts such as triphenylbenzylphosphonium chloride, tetraphenylphosphonium chloride, tetraoctylphosphonium chloride, quaternary ammonium salts such as triphenylbenzylammonium chloride, tetra- Examples include phenyl ammonium chloride and the like. (4) Other auxiliary materials include carbon black as a reinforcing agent, MgO and Ca(OH) 2 as acid acceptors,
There are plasticizers and processing aids, which are added as appropriate. <B> NBR compound: A vulcanizing agent and metal oxides selected from Group 1 of the periodic table are blended with the NBR polymer below, along with other auxiliary materials, and the vulcanization accelerator (organic phosphonium salt and/or quaternary ammonium salt) 0.1 to 2 PHR if the organic phosphonium salt is included in the polyol vulcanization compound in the FKM formulation, and 0.05 to 2 PHR if the quaternary ammonium salt is also included.
Contains 2 PHRs. Here, if the blending amount of the vulcanization accelerator is less than the lower limit value, it will be difficult to obtain a large interlayer adhesive force between the FKM layer and the NBR layer, and even if it exceeds the upper limit value, the interlayer adhesive force will not increase and it will be wasteful. be. (1) NBR is an acrylonitrile-butadiene copolymer, but from the viewpoint of oil resistance and cold resistance of the NBR layer, the bonding amount of acrylonitrile is usually 15 to 55.
% is used. Specifically, Nipole
DN101・103・202・302・206, TN103,
JSRN220S/N230S/N231H, hiker
Examples include those labeled with trade names such as 1001, 1031, and 1042. Here, “Nipole” and “hiker” are Nippon Zeon’s “JSR”
are trademarks of Japan Synthetic Rubber. (2) The vulcanization system for this NBR is not particularly limited, such as sulfur vulcanization, peroxide vulcanization, etc. Incidentally, as the peroxide vulcanizing agent, those exemplified above are used. (3) Examples of metal oxides include magnesium oxide,
Examples include aluminum oxide, zinc oxide, zinc dioxide, calcium oxide, lead oxide (,), silicon dioxide, etc., and their hydroxides. Among these, magnesium oxide, calcium hydroxide, aluminum hydroxide, lead oxide, () is preferred. The amount of these metal oxides is usually 5~
It will be 30PHR. (4) Auxiliary materials other than those mentioned above include reinforcing agents such as carbon black, vulcanization accelerators, processing aids, plasticizers, coloring agents, anti-aging agents, etc., and are blended as appropriate. <Effects of the Invention> As described above, the method for producing a rubber laminate of the present invention involves blending a specific amount of a vulcanization accelerator in the polyol vulcanization compound contained in the NBR compound as well as in the FKM compound. By doing so, during production, scorch is less likely to occur in FKM during extrusion, kneading, and calendering, and the physical properties of the material are also good. Furthermore, the interlayer adhesion of the resulting rubber laminate is also good, as shown in the examples below. It is. <Example> For each test example, the FKM layer was prepared using the formulation shown in Table 1, and the NBR layer was prepared using the formulation shown in Table 2.
The layers were rolled into sheets of 4mmt each and heated at 170°C for 15 minutes using the combinations shown in Table 3.
Pressure vulcanization was carried out under the conditions of 150 kgf/cm 2 . The adhesive strength is
Measured according to JISK6301 "Peeling test".
In addition, the scorch time (JISK6300, 145℃), normal state physical properties (JISK6301), solvent cracking resistance and low temperature impact embrittlement test (JISK6301) of each FKM and NBR
The results are shown in Tables 1 and 2. Note that solvent cracking resistance was determined using Fuel D (toluene) using a JIS dumbbell No.
60vol%/isooctane 40vol%),
The time until breakage was measured. From the results shown in Table 3, it was found that the vulcanization accelerator in the vulcanization compound of polyol vulcanization is added to NBR at a specified amount or more (0.1 PHR or more when organic phosphonium salt is added to FKM, and quaternary ammonium When salt is added (0.05PHR or more), when salt is added (N-2, 3, 4, 5, 6), FKM
It can be seen that good interlayer adhesion occurs between the layer and the NBR layer. Furthermore, Table 2 shows that even if a polyol vulcanization accelerator is added to NBR, the scorch time is not affected. As shown in Table 1, FKMs F1 to F3 and F6 to F7 all have scorch times of 7 minutes or more.
【表】【table】
【表】【table】
【表】【table】
【表】
*ゴム破壊
[Table] *Rubber destruction
第1図は本発明の製造方法を適用可能な積層体
の一例であるゴムホースの斜視図、第2図は同じ
くダイヤフラムの斜視図である。
1…フツ素ゴム層、2…NBR層、3…基布層。
FIG. 1 is a perspective view of a rubber hose, which is an example of a laminate to which the manufacturing method of the present invention can be applied, and FIG. 2 is a perspective view of a diaphragm. 1...Fluororubber layer, 2...NBR layer, 3...Base fabric layer.
Claims (1)
物(B)からなるNBR層とを加硫接着させることを
特徴とするゴム積層体の製造方法。 (A) 過酸化物加硫系のFKM配合物において、有
機ホスホニウム塩を含むポリオール加硫系の加
硫配合剤が配合されている。 (B) NBR配合物において、周期表第−族か
ら選ばれる金属酸化物(又は水酸化物)が5〜
50PHR(加硫剤として金属酸化物が含まれてい
る場合はそれに加えて)配合され、さらに有機
ホスホニウム塩及び/又は第四級アンモニウム
塩が0.1〜2PHR配合されている。 2 下記配合物(A)からなるFKM層と、下記配合
物(B)からなるNBR層とを加硫接着させることを
特徴とするゴム積層体の製造方法。 (A) 過酸化物加硫系のFKM配合物において、第
四級アンモニウム塩を含むポリオール加硫系の
加硫配合剤が配合されている。 (B) NBR配合物において、周期表−族から
選ばれる金属酸化物(又は水酸化物)が5〜
50PHR(加硫剤として金属酸化物が含まれてい
る場合はそれに加えて)配合され、さらに有機
ホスホニウム塩及び/又は第四級アンモニウム
塩が0.05〜2PHR配合されている。[Claims] 1. A method for producing a rubber laminate, which comprises vulcanizing and adhering an FKM layer made of the following compound (A) and an NBR layer made of the following compound (B). (A) A peroxide vulcanization FKM formulation contains a polyol vulcanization compound containing an organic phosphonium salt. (B) In the NBR formulation, the metal oxide (or hydroxide) selected from Group 1 of the periodic table is
50 PHR (in addition to a metal oxide if it is included as a vulcanizing agent) is blended, and 0.1 to 2 PHR of an organic phosphonium salt and/or quaternary ammonium salt is further blended. 2. A method for producing a rubber laminate, which comprises vulcanizing and adhering an FKM layer consisting of the following compound (A) and an NBR layer consisting of the following compound (B). (A) A peroxide vulcanization FKM formulation contains a polyol vulcanization compound containing a quaternary ammonium salt. (B) In the NBR formulation, the metal oxide (or hydroxide) selected from the periodic table group is 5 to 5.
50 PHR (in addition to a metal oxide if it is included as a vulcanizing agent) is blended, and 0.05 to 2 PHR of an organic phosphonium salt and/or quaternary ammonium salt is further blended.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18603185A JPS6246642A (en) | 1985-08-24 | 1985-08-24 | Manufacture of rubber laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18603185A JPS6246642A (en) | 1985-08-24 | 1985-08-24 | Manufacture of rubber laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6246642A JPS6246642A (en) | 1987-02-28 |
JPH0582812B2 true JPH0582812B2 (en) | 1993-11-22 |
Family
ID=16181182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18603185A Granted JPS6246642A (en) | 1985-08-24 | 1985-08-24 | Manufacture of rubber laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6246642A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4828923A (en) * | 1987-04-10 | 1989-05-09 | Nippon Zeon Co., Ltd. | Rubber laminates of fluororubber and nitrile rubber |
JPH0615216B2 (en) * | 1987-12-12 | 1994-03-02 | 倉敷化工株式会社 | Method for manufacturing oil resistant rubber hose |
EP0759354B1 (en) * | 1994-01-24 | 2000-08-16 | Nippon Zeon Co., Ltd. | Laminate of vulcanizable rubber composition layers, process for producing a vulcanized rubber laminate, and rubber laminate |
JP2007169511A (en) * | 2005-12-22 | 2007-07-05 | Nok Corp | Rubber composition and method for producing crosslinked fluororubber |
JP4580335B2 (en) * | 2005-12-22 | 2010-11-10 | Nok株式会社 | Method for producing cross-linked fluororubber |
EP2674305A4 (en) * | 2011-02-08 | 2015-09-09 | Bridgestone Corp | Rubber laminate, run flat tire, and pneumatic tire |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5749391A (en) * | 1980-09-08 | 1982-03-23 | Toshiba Corp | Inverter controlling circuit for driving motor |
JPS58220732A (en) * | 1982-06-18 | 1983-12-22 | 日本ゼオン株式会社 | Manufacture of laminate |
JPS5970562A (en) * | 1982-10-15 | 1984-04-21 | 豊田合成株式会社 | Rubber laminated material |
JPS6067149A (en) * | 1983-09-22 | 1985-04-17 | 日本ゼオン株式会社 | Manufacture of rubber laminate |
-
1985
- 1985-08-24 JP JP18603185A patent/JPS6246642A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5749391A (en) * | 1980-09-08 | 1982-03-23 | Toshiba Corp | Inverter controlling circuit for driving motor |
JPS58220732A (en) * | 1982-06-18 | 1983-12-22 | 日本ゼオン株式会社 | Manufacture of laminate |
JPS5970562A (en) * | 1982-10-15 | 1984-04-21 | 豊田合成株式会社 | Rubber laminated material |
JPS6067149A (en) * | 1983-09-22 | 1985-04-17 | 日本ゼオン株式会社 | Manufacture of rubber laminate |
Also Published As
Publication number | Publication date |
---|---|
JPS6246642A (en) | 1987-02-28 |
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